Aminosilyl-functionalized conjugated dienes, their preparation and their use in the production of rubbers

ABSTRACT

The invention relates to aminosilyl-functionalized conjugated dienes, their preparation and their use in the production of rubbers. Further, the invention relates to rubbers and rubber compositions, and tires produced therefrom. The functionalized conjugated dienes are selected from the group of compounds of formula (IIia), (Nib), (IIIc)

The present invention relates to aminosilyl-functionalized conjugateddienes, their preparation and their use in the production of rubbers.Further, the invention relates to rubbers and rubber compositions, andtires produced therefrom.

A variety of conjugated diene monomers is known that can be used in theproduction of synthetic rubbers. However, there is a need in the art forfurther conjugated diene monomers that can be used in advantageouspolymerization processes, or that confer advantageous properties to therubbers produced from such conjugated diene monomers.

STATE OF THE ART

P. P. Choudhury and M. E. Welker (Molecules 2015, 20, 16892-16907)report the preparation of 2-silicon-substituted 1,3-dienes via Grignardchemistry. The authors further report the use of the2-silicon-substituted 1,3-dienes in one pot metathesis/Diels-Alderreactions in regio- and diastereoselective fashions.

EP 3 159 346 A1 teaches aminosilane-functionalized diene compounds thatare useful as modifying monomers in the polymerization of conjugateddiene monomers, optionally together with aromatic vinyl monomers, thusproducing polymers, specifically elastomeric polymers, which can be usedin rubber articles such as tires.

WO2016/162473 A1 and WO2016/162528 A1 disclose aminosilyl-functionalizedstyrenes and methods for their preparation, as well as the use of thestyrene derivatives in the preparation of copolymers thereof.

EP 3 064 546 A1 teaches the use of vinylsilanes in the production ofrubbers. EP 2 857 446 A1 teaches a conjugated diene polymer derived fromconjugated diene, a monomer unit V¹-S¹, and a monomer unit V²-A², whereV¹ and V² each represent a hydrocarbyl group containing a polymerizablecarbon-carbon double bond, S¹ represents a substituted silyl group, andA² is an amino group or a nitrogen-containing heterocycle group.

Accordingly, it was an object of the invention to provide conjugateddiene monomers for the production of synthetic rubbers. These conjugateddiene monomers should be based on easily accessible starting materials,and should be accessible via simple synthetic routes. Moreover, theconjugated diene monomers should be universally applicable, i.e. in avariety of different polymerization processes, and should conferadvantageous properties to the rubbers, rubber compositions, and tiresproduced therefrom.

It has now surprisingly been found in accordance with the presentinvention that this object is solved by the use of specific conjugateddienes having aminosilyl functionalization. The functionalizedconjugated dienes of the invention are selected from the group ofcompounds of formulae (IIIa), (IIIb), (IIIc)

-   -   wherein    -   R is an organylene group optionally containing one or more        heteroatoms selected from an oxygen atom, a sulfur atom, a        nitrogen atom, and a silicon atom, and the starting conjugated        diene selected from the group of compounds of formula (Ia),        (Ib), (Ic)

-   -   from which the functionalized conjugated diene of formula        (IIIa), (IIIb), (IIIc) is derived, has at least 10 carbon atoms,    -   R¹ is selected from        -   i) a single bond,        -   ii) one or more of an oxygen atom, a sulfur atom, a group            NR⁶, and a group SiR⁷R⁸; and        -   iii) an organylene group optionally containing one or more            selected from an oxygen atom, a sulfur atom, a group NR⁶,            and a group SiR⁷R⁸;    -   R², R³, R⁶, R⁷, R⁸ can be the same or different and represent an        organyl group optionally containing one or more heteroatoms        selected from an oxygen atom, a sulfur atom, a nitrogen atom,        and a silicon atom; and    -   i) R⁴ and R⁵ can be the same or different and each R⁴ and R⁵        independently represents an organyl group optionally containing        one or more heteroatoms selected from a silicon atom, an oxygen        atom, a sulfur atom, and a nitrogen atom;

or

-   -   ii) R⁴ and R⁵ are bonded to each other to form a heterocyclic        ring containing the nitrogen atom and at least one carbon atom        and, optionally, one or more heteroatoms selected from a silicon        atom, an oxygen atom, a sulfur atom, and a nitrogen atom.

The functionalized conjugated dienes of the invention, when used e.g. inthe production of solution styrene butadiene rubber (S-SBR) andZiegler-Natta catalyzed (e.g. neodymium) butadiene rubber (Nd-BR),increase the interaction of the polymer with fillers and thus fillerdispersion in the polymer matrix, helping to improve the dynamic andmechanical properties of tire tread compounds.

In a first aspect, the present invention relates to methods for thepreparation of a functionalized conjugated diene.

In a second aspect, the invention relates to the functionalizedconjugated diene.

In a third aspect, the invention relates to the use of thefunctionalized conjugated dienes in the production of an elastomericcopolymer.

In a fourth aspect, the invention relates to a process for theproduction of copolymer component comprising coupled copolymer andterminally modified copolymer.

In a fifth aspect, the invention relates to a process for producing anelastomeric copolymer comprising anionic polymerization conditions.

In a sixth aspect, the invention relates to a process for producing anelastomeric copolymer comprising Ziegler-Natta polymerizationconditions.

In a seventh aspect, the invention relates to an elastomeric copolymer.

In an eighth aspect, the invention relates to a method for producing arubber.

In a ninth aspect, the invention relates to a rubber.

In a tenth aspect, the invention relates to a rubber composition.

In an eleventh aspect, the invention relates to a tire component.

Finally, in a twelfth aspect, the invention relates to a tire.

DETAILED DESCRIPTION OF THE INVENTION

In a first embodiment of the first aspect, the invention relates to amethod for the preparation of a functionalized conjugated diene selectedfrom the group of compounds of formula (IIIa), (IIIb), (IIIc)

-   -   wherein    -   R is an organylene group optionally containing one or more        heteroatoms selected from an oxygen atom, a sulfur atom, a        nitrogen atom, and a silicon atom, and the starting conjugated        diene selected from the group of compounds of formula (Ia),        (Ib), (Ic)

-   -   from which the functionalized conjugated diene of formula        (IIIa), (IIIb), (IIIc) is derived, has at least 10 carbon atoms,    -   R¹ is selected from        -   i) a single bond,        -   ii) one or more of an oxygen atom, a sulfur atom, a group            NR⁶, and a group SiR⁷R⁸; and        -   iii) an organylene group optionally containing one or more            selected from an oxygen atom, a sulfur atom, a group NR⁶,            and a group SiR⁷R⁸;    -   R², R³, R⁶, R⁷, R⁸ can be the same or different and represent an        organyl group optionally containing one or more heteroatoms        selected from an oxygen atom, a sulfur atom, a nitrogen atom,        and a silicon atom; and    -   i) R⁴ and R⁵ can be the same or different and each R⁴ and R⁵        independently represents an organyl group optionally containing        one or more heteroatoms selected from a silicon atom, an oxygen        atom, a sulfur atom, and a nitrogen atom;    -   or    -   ii) R⁴ and R⁵ are bonded to each other to form a heterocyclic        ring containing the nitrogen atom and at least one carbon atom        and, optionally, one or more heteroatoms selected from a silicon        atom, an oxygen atom, a sulfur atom, and a nitrogen atom,

the method comprising reacting, under Grignard conditions, a conjugateddiene halide selected from the group of compounds of formula (IIIa),(IIIb), (IIc)

wherein Y¹ is selected from fluorine, chlorine, bromine, and iodineatoms (and Y¹ is preferably a chlorine atom),

with a compound of formula (IV)

wherein Y² is selected from fluorine, chlorine, bromine, and iodineatoms.

In a second embodiment of the first aspect, the invention relates to amethod for the preparation of a functionalized conjugated diene selectedfrom the group of compounds of formula (IIIa), (IIIb), (IIIc), themethod comprising

-   -   A) reacting, under Grignard conditions, a conjugated diene        halide selected from the group of compounds of formula (IIa),        (IIb), (IIc)    -   with a compound of formula (V)

-   -   wherein Y² and Y³ are independently selected from fluorine,        chlorine, bromine, and iodine atoms, and preferably Y² and rare        each chlorine atoms, to result in a compound of formula (VIa),        (VIb), (VIc)

-   -   and    -   B) reacting the compound of formula (VIa), (VIb), (VIc) with an        amide of formula (VII)

-   -   wherein M is an alkali metal selected from lithium, sodium and        potassium, and M is preferably sodium.

The preparation of the conjugated diene halide intermediate of formula(IIa), (IIb), (IIc) wherein Y¹ is a chlorine atom may be performed usinga chlorinating agent comprising trichloroisocyanuric acid,dichloroisocyanuric acid, an alkali metal salt of dichloroisocyanuricacid, or a mixture thereof. Further details regarding the synthesis ofthis conjugated diene chloride intermediate are given inPCT/EP2018/070768.

The functionalized conjugated diene of the second aspect of theinvention is selected from the group of compounds of formula (IIIa),(IIIb), (IIIc)

-   -   wherein    -   R is an organylene group optionally containing one or more        heteroatoms selected from an oxygen atom, a sulfur atom, a        nitrogen atom, and a silicon atom, and the starting conjugated        diene selected from the group of compounds of formula (Ia),        (Ib), (Ic)

-   -   from which the functionalized conjugated diene of formula        (IIIa), (IIIb), (IIIc) is derived, has at least 10 carbon atoms,    -   R¹ is selected from        -   a single bond,        -   ii) one or more of an oxygen atom, a sulfur atom, a group            NR⁶, and a group SiR⁷R⁵; and        -   iii) an organylene group optionally containing one or more            selected from an oxygen atom, a sulfur atom, a group NR⁶,            and a group SiR⁷R⁵;    -   R², R³, R⁶, R⁷, R⁸ can be the same or different and represent an        organyl group optionally containing one or more heteroatoms        selected from an oxygen atom, a sulfur atom, a nitrogen atom,        and a silicon atom; and    -   i) R⁴ and R⁵ can be the same or different and each R⁴ and R⁵        independently represents an organyl group optionally containing        one or more heteroatoms selected from a silicon atom, an oxygen        atom, a sulfur atom, and a nitrogen atom;

or

-   -   ii) R⁴ and R⁵ are bonded to each other to form a heterocyclic        ring containing the nitrogen atom and at least one carbon atom        and, optionally, one or more heteroatoms selected from a silicon        atom, an oxygen atom, a sulfur atom, and a nitrogen atom.

In the description of the present invention, an organyl group is anyorganic substituent group, regardless of functional type, having onefree valence at a carbon atom. Preferably, an organyl group containsfrom 1 to 10 carbon atoms, and optionally one or more heteroatomsselected from a silicon atom, an oxygen atom, a sulfur atom, and anitrogen atom, or an aryl, heteroaryl or aralkyl group containing from 6to 10 carbon atoms, and optionally one or more heteroatoms selected froma silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom.

Also, an organylene group is any organic substituent group, regardlessof functional type, having two free valences at one carbon atom, or onefree valence at each of two carbon atoms.

Preferably, R¹ of the functionalized conjugated diene of the presentinvention is i) a single bond.

Preferably, R², R³, R⁶, R⁷, R⁸ may be the same or different andrepresent an organyl group containing from 1 to 10 carbon atoms, andoptionally one or more heteroatoms selected from a silicon atom, anoxygen atom, a sulfur atom, and a nitrogen atom, or an aryl, heteroarylor aralkyl group containing from 6 to 10 carbon atoms, and optionallyone or more heteroatoms selected from a silicon atom, an oxygen atom, asulfur atom, and a nitrogen atom.

It is further preferred that R², R³, R⁶, R⁷, and R⁸ are the same ordifferent and represent a linear or branched, saturated or unsaturatedhydrocarbyl group (preferably containing from 1 to 10 carbon atoms).Further preferably, R², R³, R⁶, R⁷, and R⁸ are the same or different andrepresent a linear or branched alkyl, aryl, or alkaryl group; morepreferably, R², R³, R⁶, R⁷, and R⁸ are the same or different andrepresent CH₃ or C₆H₅, in particular R², R³, R⁶, R⁷, and R⁸ allrepresent CH₃.

According to the invention, R⁴ and R⁵ are each a group that at least hasa carbon atom bound to the nitrogen atom, i.e. groups R⁴ and R⁵ are notbound to the nitrogen atom via any heteroatom that may optionally bepresent in R⁴ or R⁵.

In embodiment i), R⁴ and R⁵ can be the same or different and each R⁴ andR⁵ independently represents a linear, branched or cyclic hydrocarbylgroup containing from 1 to 10 carbon atoms, the hydrocarbyl groupoptionally containing at least one heteroatom selected from a siliconatom, an oxygen atom, and a nitrogen atom; the hydrocarbyl group issaturated or unsaturated.

Preferably, i) R⁴ and R⁵ are the same or different and each R⁴ and R⁵independently represents a linear, branched or cyclic, saturated orunsaturated alkyl group containing from 1 to 10 carbon atoms, the alkylgroup optionally containing one or more heteroatoms selected from asilicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom; or ii)R⁴ and R⁵ are the same or different and each R⁴ and R⁵ independentlyrepresents an aryl or aralkyl group containing from 6 to 10 carbonatoms, the alkyl group optionally one or more heteroatoms selected froma silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom.

It is preferred that R⁴ and R⁵ are the same and represent a linear,branched or cyclic, saturated or unsaturated alkyl group. Morepreferably, R⁴ and R⁵ are the same and represent —CH(CH₃)₂ or CH₃. Mostpreferably, R⁴ and R⁵ are the same and represent —CH(CH₃)₂.

The conjugated diene selected from the group of compounds of formula(Ia), (Ib), (Ic)

from which the functionalized conjugated diene of formula (IIIa),(IIIb), (IIIc) is derived has at least 10 carbon atoms. Preferably, R isa linear or branched, saturated or unsaturated hydrocarbylene,hydrocarbylidene, or hydrocarbylidyne group; more preferably, R is abranched, unsaturated hydrocarbylene group; most preferably, theconjugated diene of formula (IIa), (IIb), (IIc) is selected fromterpenes and 4,8-dimethyl-1,3,7-nonatriene. Even more preferably, theterpene is selected from myrcene and ocimene, most preferably theterpene is myrcene selected from α-myrcene and β-myrcene.

The functionalized conjugated diene according to the invention is in allaspects most preferably a myrcene derivative of formula (VIII), (IX), or(X)

In particular, the myrcene derivative is of formula (VIIIa), (IXa), or(Xa)

In a third aspect, the present invention relates to the use of one ormore functionalized conjugated dienes of the second aspect in theproduction of an elastomeric copolymer. The elastomeric copolymerpreferably comprises, in addition to one or more units derived from theone or more functionalized conjugated dienes selected from the group ofcompounds of formula (IIIa), (IIIb), (IIIc), units derived from one ormore conjugated diene monomers.

The conjugated diene monomer as used in the production of theelastomeric copolymer according to the third aspect of the invention ispreferably selected from 1,3-butadiene, isoprene, 1,3-pentadiene,2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene,2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, and4,5-diethyl-1,3-octadiene. More preferably, the conjugated diene monomeris selected from 1,3-butadiene and isoprene, in particular, theconjugated diene monomer is 1,3-butadiene.

Preferably, the use according to the third aspect is in the productionof an elastomeric copolymer by 1) anionic polymerization or by 2)coordination polymerization.

It is preferred that the elastomeric copolymer further comprises unitsderived from one or more vinyl aromatic monomers. The vinyl aromaticmonomer is preferably selected from styrene, 1-vinylnaphthalene,3-methyl styrene, 3,5-diethylstyrene, 4-propylstyrene,2,4,6-trimethylstyrene, 4-dodecylstyrene, 3-methyl-5-n-hexylstyrene,4-phenylstyrene, 2-ethyl-4-benzylstyrene, 3,5-diphenylstyrene,2,3,4,5-tetraethylstyrene, 3-ethyl-1-vinylnaphthalene,6-isopropyl-1-vinylnaphthalene, 6-cyclohexyl-1-vinylnaphthalene,7-dodecyl-2-vinylnaph-thalene, and α-methyl styrene. More preferably,the vinyl aromatic monomer is selected from styrene, 3-methylstyrene,and α-methylstyrene. In particular, the vinyl aromatic monomer isstyrene.

According to the invention, the amount of units derived from the one ormore functionalized conjugated dienes selected from of the group ofcompounds of formula (IIIa), (IIIb), (IIIc) is preferably in a range offrom 0.05 to 5 wt. %, based on the weight of the elastomeric copolymer,more preferably in a range of from 0.2 to 1.5 wt. %, most preferably ina range of from 0.4 to 1.2 wt. %, e.g. in a range of from 0.6 to 1.0 wt.%, such as about 0.8 wt. %.

The use according to the third aspect may be of an alkali metal saltderivative of the functionalized conjugated diene selected from thegroup of compounds of formula (IIIa), (IIIb), (IIIc), as initiator forthe anionic copolymerization of one or more conjugated diene monomers,optionally one or more vinyl aromatic monomers, and optionally one ormore functionalized conjugated dienes selected from the group ofcompounds of formula (IIIa), (IIIb), (IIIc).

In a fourth aspect, the invention relates to a process for theproduction of a copolymer component comprising coupled copolymer andterminally modified copolymer, the process comprising the followingsteps:

-   -   (1) providing an initiator component, wherein the initiator        component preferably comprises one or more alkali metal salt        derivatives of a one or more functionalized conjugated dienes        selected from the group of compounds of formula (IIIa), (IIIb),        (IIIc),    -   (2) contacting a monomer component comprising        -   i) one or more functionalized conjugated dienes selected            from the group of compounds of formula (IIIa), (IIIb),            (IIIc),        -   ii) one or more conjugated diene monomers and        -   iii) optionally one or more vinyl aromatic monomers,        -   with the initiator component, to initiate anionic            copolymerization;    -   (3) continuing copolymerization, to result in a copolymer;    -   (4) optionally continuing copolymerization of the copolymer, in        the presence of one or more functionalized monomers, to result        in a functionalized copolymer;    -   (5) optionally coupling a part of the copolymer of step (3) or        the functionalized copolymer of step (4) with one or more        coupling agents, to result in coupled copolymer; and    -   (6) optionally terminally modifying a part of the copolymer of        step (3) or the functionalized copolymer of step (4) with one or        more terminal modifying agents, to result in terminally modified        copolymer.

In a fifth aspect, the invention relates to a process for producing anelastomeric copolymer comprising subjecting

-   -   i) one or more functionalized conjugated dienes selected from        the group of compounds of formula (IIIa), (IIIb), (IIIc),    -   ii) one or more conjugated diene monomers, and    -   iii) optionally one or more vinyl aromatic monomers

to anionic polymerization conditions. Preferably, the anionicpolymerization conditions include initiating the polymerization with analkali metal salt derivative of the one or more functionalizedconjugated dienes of formula (IIIa), (IIIb), (IIIc), wherein the alkalimetal is selected from lithium, sodium, and potassium.

Using anionic polymerization, copolymers having a linear structure or astar structure may be obtained. Also, branching may be performed withe.g. divinylbenzene. The branching level is difficult to predict sinceit is difficult to fractionate the specific polymer fractions. Thus, itis more appropriate to define the copolymers as obtained by anionicpolymerization by their dispersity index, M_(w)/M_(n), which istypically as follows:

-   -   Linear copolymer: 1.01 to 2.0;    -   Coupled copolymer: 1.1 to 3; and    -   Branched copolymer: 1.1 to 8.0.

According to the sixth aspect, the invention relates to a process forproducing an elastomeric copolymer comprising subjecting

-   -   i) one or more functionalized conjugated dienes selected from        the group of compounds of formula (IIIa), (IIIb), (IIIc)

and

-   -   ii) one or more conjugated diene monomers

to Ziegler-Natta polymerization conditions.

In the coordination polymerization of conjugated diene (such as1,3-butadiene), a Ziegler-Natta catalyst is used. Typical catalystcompositions are binary, ternary, or quaternary systems. Binary systemscomprise catalytic metal chloride (e.g. chloride of Ni, Co, Ti, Nd, V,Ti, Zr, or Fe) and co-catalyst (e.g. aluminum alkyl or a magnesium alkylcompound). In ternary catalyst systems, a halide-free metal precursor(such as neodymium phosphate) is combined with a co-catalyst (such asaluminium or magnesium alkyl) and a halide donor. Adding halide donorsto halide-free catalyst systems significantly increases catalystactivities and cis-1,4 or trans-1,4 contents. In quaternary catalystsystems, a solubilizing agent for either the metal-salt or for thehalide donor is used, in addition to the components as used in ternarysystems.

The Ziegler-Natta polymerization conditions consequently preferablyinclude a catalyst system comprising 1) metal chloride and 2)co-catalyst. More preferably, the metal chloride 1) is selected fromchlorides of one or more of Ni, Co, Ti, Nd, V, Ti, Zr, and Fe, and theco-catalyst 2) is selected from one or more of aluminium and magnesiumalkyl compounds.

Also, the Ziegler-Natta polymerization conditions may include thepresence of further monomers.

It is alternatively preferred that the Ziegler-Natta polymerizationconditions include a catalyst system comprising 1) non-halide metalcompound, 2) co-catalyst, and 3) halide donor compound. The non-halidemetal compound 1) is preferably one or more Nd compounds; morepreferably the Nd compound is selected from neodymium carboxylates,neodymium alcoholates, neodymium phosphates, neodymium phosphonates,neodymium allyl compounds, neodymium cyclopentadienyl complexes,neodymium amides, and neodymium acetylacetonates.

The most effective catalysts for the production of high cispolybutadiene are ternary systems based on neodymium, where catalystprecursors such as 1) neodymium carboxylates (e.g.neodymium(III)versatate (NdV), neodymium(III) octanoate (NdO),neodymium(III) isooctanoate (NdiO), neodymium(III) naphthenate (NdN); 2)neodymium alcoholates (e.g. Nd(OBu)₃, Nd(OiPr)₃); 3) neodymiumphosphates and phosphonates (e.g. neodymium bis(2-ethylhexyl)phosphate(NdP), bis(2-ethylhexanol)phosphonate); 4) neodymium allyl compounds; 5)neodymium cyclopentadienyl complexes (e.g. monocyclopentadienylneodymium dichloride (CpNdCl₂), monocyclopentadienyl dialkyl neodymium(CpNdR₂), monocyclopentadienyl diallyl neodymium (CpNd(η₃-C₃H₅)₂), saltsof monoclopentadienyl tris allyl neodymium (e.g Li[CpNd(η₃-C₃H₅)₃]),dicyclopentadienyl neodymium monochloride (Cp₂NdCl), dicyclopentadienylmonoalkyl neodymium (Cp₂NdR), silylene-bridged dicyclopentadienylneodymium derivatives (e.g. [R₂Si(Cp)₂]Nd(CIiR)); 6) neodymium amides(e.g. Nd(N(SiMe₃)₂)₃); or 7) neodymium acetylacetonates are used, incombination with one or more co-catalyst such as: AlMe3 (TMA), AlEt₃(TEA), AliBu₃ (TIBA), AlOct₃, methyl alumoxane (MAO), tetraisobutyldialumoxane (TIBAO), B(C₆F₅)₃, modified methyl alumoxane (MMAO),hexaisobutylalumoxane (HIBAO), diisobutylaluminum hydride (DIBAH), MgR₂,AlPr₃, AlBu₃, AlHex₃, AlOct₃, AlDodec₃, AlEt₃, or AlMe₃.

Examples for halide donors are SiCl₄, ethylaluminium sesquichloride(EASC), diethylaluminium chloride (DEAC), dimethylaluminium chloride,butyl chloride (BuCI), dibutylaluminium chloride, AlBr₃, EtAlCl₂, andMe₃SiCl.

The copolymer as produced in accordance with the sixth aspect, i.e. bycoordination polymerization, preferably has linear structure or branchedstructure. The polymer structure is dictated by catalyst composition andis typically as follows (M_(w)/M_(n)):

-   -   Linear copolymer: 1.5 to 5.0,    -   Branched copolymer: 1.5 to 20.0.

According to the seventh aspect, the invention relates to an elastomericcopolymer comprising repeat units that are derived from

-   -   A) 0.05 wt. % to 5 wt. %, by weight of the copolymer, of one or        more functionalized conjugated dienes selected from the group of        compounds of formula (IIIa), (IIIb), (IIIc);    -   B) 45 wt. % to 99.95 wt. %, by weight of the copolymer, of one        or more conjugated diene monomers;    -   C) 0 wt. % to 50 wt. %, by weight of the copolymer, of one or        more vinyl aromatic monomers.

The amount of B) conjugated diene monomer in the elastomeric copolymerof the seventh aspect is preferably 50 to 92 wt. %, by weight of thecopolymer, more preferably 60 to 90 wt. %, by weight of the copolymer,in particular 65 to 80 wt. %, by weight of the copolymer.

The vinyl aromatic monomer, when present, is preferably selected fromstyrene, 1-vinylnaphthalene, 3-methylstyrene, 3,5-diethylstyrene,4-propylstyrene, 2,4,6-trimethylstyrene, 4-dodecylstyrene,3-methyl-5-n-hexylstyrene, 4-phenylstyrene, 2-ethyl-4-benzylstyrene,3,5-diphenylstyrene, 2,3,4,5-tetraethylstyrene,3-ethyl-1-vinylnaphthalene, 6-isopropyl-1-vinylnaphthalene,6-cyclohexyl-1-vinylnaphthalene, 7-dodecyl-2-vinylnaphthalene, andα-methylstyrene. More preferably, the vinyl aromatic monomer is selectedfrom styrene, 3-methylstyrene and α-methylstyrene. In particular, thevinyl aromatic monomer is styrene.

The amount of C) vinyl aromatic monomer in the elastomeric copolymeraccording to the seventh aspect of the present invention is preferably 8to 45 wt. %, by weight of the copolymer, more preferably 10 to 40 wt. %,by weight of the copolymer, in particular 20 to 35 wt. %, by weight ofthe copolymer.

Alternatively, the elastomeric copolymer comprises less than 1 wt. % C)vinyl aromatic monomer (and preferably no C) vinyl aromatic monomer),and the amount of B) conjugated diene monomer is 95 to 99.95 wt. %, byweight of the copolymer, preferably 98 to 99.6 wt. %, by weight of thecopolymer, in particular 99.0 to 99.4 wt. %, by weight of the copolymer.

The conjugated diene monomer in the elastomeric copolymer according tothe seventh aspect is preferably selected from 1,3-butadiene, isoprene,1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene,2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, and4,5-diethyl-1,3-octadiene. More preferably, the conjugated diene monomeris selected from 1,3-butadiene and isoprene. The conjugated dienemonomer is in particular 1,3-butadiene.

The elastomeric copolymer according to the invention may comprise unitshaving a linear structure.

Also, the copolymer may comprise units having a branched structure.

Moreover, the elastomeric copolymer may comprise units having a starstructure and being produced by the reaction of metal-terminated livinglinear copolymer with one or more coupling agents in anionicpolymerization conditions. The coupling agent may be

-   -   I) a tin halide coupling agent (preferably the tin halide        coupling agent is tin tetrachloride), or    -   II) a silicon halide coupling agent (preferably the silicon        halide coupling agent is selected from silicon tetrachloride,        silicon tetrabromide, silicon tetrafluoride, silicon        tetraiodide, hexachlorodisilane, hexabromodisilane,        hexafluorodisilane, hexaiododisilane, octachlorotrisilane,        octabromotrisilane, octafluorotrisilane, octaiodotrisilane,        hexachlorodisiloxane,        2,2,4,4,6,6-hexachloro-2,4,6-trisilaheptane-1,2,3,4,5,6-hexakis[2-(methyldichlorosilyl)ethyl]benzene,        and alkyl silicon halides of general formula (XI)

R⁶ _(n)—Si—X_(4-n)   (XI),

-   -   wherein R⁶ is a monovalent aliphatic hydrocarbon group having 1        to 20 carbon atoms or a monovalent aromatic hydrocarbon group        having 6 to 18 carbon atoms; n is an integer of 0 to 2; and X        can be a chlorine, bromine, fluorine or iodine atom).

In the elastomeric copolymer according to the seventh aspect, thefraction of units having star structure is preferably between 0 and 75%,by weight of the copolymer.

According to the eighth aspect, the invention relates to a method forproducing a rubber comprising vulcanizing the elastomeric copolymeraccording to the seventh aspect in the presence of one or morevulcanizing agents.

According to an ninth aspect, the invention relates to a rubber asobtainable according to the method of the eighth aspect.

According to a tenth aspect, the invention relates to a rubbercomposition comprising x) a rubber component comprising the rubberaccording to the ninth aspect. Preferably, the rubber compositionfurther comprises y) one or more fillers. The filler is preferablyselected from the group consisting of silica and carbon black. Mostpreferably, the rubber composition comprises y) both silica and carbonblack.

In a preferred embodiment of the tenth aspect, the amount of fillercomponent y) in the rubber composition is 10 to 150 parts by massrelative to 100 parts by mass of the rubber component x) (phr).Preferably, the amount of filler component y) is 20 to 140 phr. Morepreferably, the amount of filler component y) is 30 to 130 phr.

Preferably, the rubber component x) in the rubber composition accordingto the tenth aspect additionally comprises one or more further rubberypolymers. It is preferred that the further rubbery polymer is selectedfrom the group consisting of natural rubber, synthetic isoprene rubber,butadiene rubber, styrene-butadiene rubber, ethylene-α-olefin copolymerrubber, ethylene-α-olefin-diene copolymer rubber,acrylonitrile-butadiene copolymer rubber, chloroprene rubber andhalogenated butyl rubber.

The tire component according to the eleventh aspect of the inventioncomprises the rubber composition according to the tenth aspect.Preferably, the tire component is a tire tread.

The tire according to the twelfth aspect of the invention comprises thetire component of the eleventh aspect.

The advantages of the present invention become more apparent from thefollowing examples. Unless indicated otherwise, all percentages aregiven by weight.

EXAMPLES

I. Synthesis of Monomers

Example 1a

A reactor of 1 L capacity, equipped with a magnetic stirrer, a droppingfunnel and a reflux condenser equipped with a gas introductionattachment and an oil valve (Zaitsev washer), was in an argon atmosphereloaded with magnesium metal (13.2 g, 0.55 mol), followed by the additionof dry and deoxygenated tetrahydrofuran (THF, 200 mL) anddiisobutylaluminium hydride (DIBAH) [(i-Bu)₂AlH, 1 mL, 5.61 mmol]. Thiswas done at room temperature, with stirring of the reactor contents. Theactivation of magnesium was conducted until evolution of hydrogenbubbles ceased. Then, (N,N-diisopropylamino)dimethylchlorosilane (96.89g, 0.50 mol) and the remaining part (300 mL) of the solvent were addedto the activated magnesium metal. The dropping funnel was filled withchloromyrcene (90.46 g, 0.53 mol). At the initiation step of thereaction, 8.00 mL of chloromyrcene were added dropwise into the mixture(without stirring the reactor contents). When clear symptoms of thereaction proceeding were observed, dosing of the remaining amount ofchloromyrcene began with such a rate that the reactor contents boiledgently for about 2 hours. After the dosing of chloromyrcene wascompleted, the reactor temperature was maintained in the range of 40° C.for one hour, followed by cooling to room temperature. To neutralize asmall excess of Grignard reagent, 0.6 mL of water were added. Then, thesolvent was evaporated from the post-reaction mixture under reducedpressure and 1.0 L of n-hexane were added to the reaction residue. Theobtained suspension was filtered off and the precipitate was washed withthree portions of n-hexane of 200 mL each. Then, the solvent wasevaporated from the obtained filtrate under reduced pressure at 40° C.until a constant pressure was achieved. 146.30 g of product wereobtained, with a yield of 91%.

GC-MS: 43 (2.85), 59 (13.97), 73 (12.42), 86 (2.46), 100 (4.14), 116(37.16), 151 (1.84), 158 (100.00), 159 (14.65), 278 (0.64), 293 (0.35)

II. Synthetic Examples for Functionalized Rubbers

II.1 Application of Functionalized Myrcene in Anionic Polymerization

In order to provide more details about the synthesis and properties ofelastomers produced according to the present invention, functionalizedstyrene-butadiene copolymers with exactly controlled micro- andmacrostructure and with functional groups are described in Examples 2b,3b and 4b below, and are compared with a non-functionalized copolymer asdescribed in Comparative Example 1 b.

Polymerization

Inertization Step:

Cyclohexane (1.2 kg) was added to a nitrogen-purged two-liter reactorand treated with 1 gram of 1.6 M n-butyllithium solution in cyclohexane.The solution was heated to 70° C. and vigorously stirred for 10 minutes,to perform cleaning and inertization of the reactor. After that, solventwas removed via a drain valve and nitrogen was purged again.

Example 1b (Comparative)

Cyclohexane (820 g) was added to the inerted two-liter reactor, followedby addition of styrene (31 g) and of 1,3-butadiene (117 g). Inhibitorfrom styrene and 1,3 butadiene was removed. Next,tetramethylethylenediamine (TMEDA, 2.21 mmol) was added, to providerandom incorporation of styrene monomer and to increase the vinylcontent, from the butadiene-derived units. The solution inside thereactor was heated to 60° C. and continuously stirred during the wholeprocess. When the desired temperature was reached, n-butyllithium (0.045mmol) was added, to perform quenching of residual impurities. Then,n-butyllithium (0.845 mmol) was added to initiate the polymerizationprocess. The reaction was carried out as a isothermic process for 60minutes. After this time, silicon tetrachloride (5.25×10⁻² mmol) wasadded to the polymer solution as a coupling agent. Coupling wasperformed for 5 minutes. The reaction solution was terminated, usingnitrogen-purged isopropyl alcohol (1 mmol), and rapidly stabilized byaddition of 2-methyl-4,6-bis(octylsulfanylmethyl)phenol (at 1.0 phrpolymer). The polymer solution was treated with isopropanol, andprecipitation of polymer occurred. The final product was dried overnightin a vacuum oven.

Example 2b Myrcene Derivative from Example as Comonomer

Cyclohexane (820 g) was added to the inerted two-liter reactor, followedby addition of styrene (31 g), functionalized myrcene of Example la(0.59 g) and 1,3-butadiene (117 g). Inhibitor from styrene and1,3-butadiene was removed. Next, 2,2-Bis(2-tetrahydrofuryl)propane(DTHFP, 2.52 mmol) was added, to provide random incorporation of styrenemonomer and to increase the vinyl content, from the butadiene-derivedunits. The solution inside the reactor was heated to 60° C. andcontinuously stirred during the whole process. When the desiredtemperature was reached, n-butyllithium (0.045 mmol) was added, toperform quenching of residual impurities. Then, n-butyllithium (0.845mmol) was added to initiate the polymerization process. The reaction wascarried out as a isothermic process for 60 minutes. After this time,silicon tetrachloride (6.30×10⁻² mmol) was added to the polymer solutionas a coupling agent. Coupling was performed for 5 minutes. The reactionsolution was terminated, using nitrogen-purged isopropyl alcohol (1mmol), and rapidly stabilized by addition of2-methyl-4,6-bis(octylsulfanylmethyl)phenol (at 1.0 phr polymer). Thepolymer solution was treated with isopropanol, and precipitation ofpolymer occurred. The final product was dried overnight in a vacuumoven.

Example 3b Myrcene Derivative from Example 1a as Both InitiatorComponent and as Comonomer

Cyclohexane (820 g) was added to the inerted two-liter reactor, followedby addition of styrene (31 g), functionalized myrcene of Example 1a(0.59 g) and 1,3-butadiene (117 g). Inhibitor from styrene and1,3-butadiene was removed. Next, 2,2-Bis(2-tetrahydrofuryl)propane(DTHFP, 3.69 mmol) was added as a styrene randomizer and to increase thevinyl content, from the butadiene-derived units. The solution inside thereactor was heated to 60° C. and continuously stirred during the wholeprocess. When the temperature was reached, n-butyllithium (0.045 mmol)was added to the reactor, to perform quenching of residual impurities.

n-Butyllithium (1.23 mmol) and functionalized myrcene of Example 1a(0.38 g) were mixed together in a burette, the contact time was about 15min, and then the mixture was added to initiate the polymerizationprocess. The reaction was carried out over 60 minutes, as an isothermicprocess. After this time, silicon tetrachloride (6.30×10⁻² mmol) wasadded to the polymer solution as a coupling agent. Coupling wasperformed for 5 minutes. The reaction solution was terminated, usingnitrogen-purged isopropyl alcohol (1 mmol), and rapidly stabilized byaddition of 2-methyl-4,6-bis(octylsulfanylmethyl)phenol (at 1.0 phrpolymer). The polymer solution was treated with isopropanol, andprecipitation of polymer occurred. The final product was dried overnightin a vacuum oven.

Example 4b Continuous Polymerization

A butadiene-styrene copolymer was prepared in a cascade of threecontinuous reactors having a volume of 10 L (reactor 1), 20 L (reactor2) and 10 L (reactor 3), respectively, where each reactor was equippedwith a paddle stirrer. The agitation speed was 150-200 rpm and fillingfactor at the level of 50%-60%. Hexane, styrene, 1,3-butadiene,1,2-butadiene (gel formation prevention additive), DTHFP andfunctionalized myrcene of Example 1a (the last three reactants assolutions in hexane) were dosed into the first reactor, with flow ratesof 10752.00 g/h, 398.00 g/h, 1499.00 g/h, 19.00 g/h, 102.00 g/h and46,03 g/h, respectively. n-Butyllithium flow rate (as a solution inhexane) was 107.00 g/h, and functionalized myrcene of Example 1a (as asolution in hexane) flow rate was 153,92 g/h. Streams of n-butyllithiumand 50/50 by weight of functionalized myrcene of Example 1a were mixedtogether in the pipe static mixer, before entering the reactor, and thecontact time was about 15 min. The temperature in the reactors wasbetween 70° C. to 85° C. To obtain branched rubber silicon tetrachloridewas added at the reactor 3 inlet, at the entry of static mixer, in aSiCl₄/active n-butyllithium ratio of 0.05. The coupling reaction wasperformed at 70-85° C. At the reactor 3 outlet,2-methyl-4,6-bis(octylsulfanylmethyl)phenol (as a solution in hexane)was added as an antioxidant (142 g/h).

The polymer solution was subsequently transferred to a stripper.Distilled water, in an amount of double of the total mass of polymersolution, as well as pH regulator and soap were added to the polymersolution, and the stripper contents were then treated with steam.Steam-stripping was carried out until the entire amount of solvent hadbeen removed, and rubber crumbs were obtained. Then, the rubber crumbswere removed from the stripper, cooled to room temperature, milled anddried in a stream of hot air.

Characterization

Vinyl Content (%)

Determined by 600 MHz ¹H-NMR, based on BS ISO 21561:2005.

Bound Styrene Content (%)

Determined by 600 MHz ¹H-NMR, based on BS ISO 21561:2005.

Molecular Weight Determination

Gel permeation chromatography was performed via PSS Polymer StandardsService multiple columns (with guard column) using THF as the eluent andfor sample preparation. Multi-angle laser light scattering measurementswere carried out using a Wyatt Technologies Dawn Heleos II lightscattering detector, DAD (PDA) Agilent 1260 Infinity UV-VIS detector andAgilent 1260 Infinity refractive index detector.

Glass Transition Temperature (° C.)

Determined based on PN-EN ISO 11357-1:2009.

Mooney viscosity (ML (1+4)/100° C.)

Determined based on ASTM D 1646-07, using a large rotor under theconditions of pre-heating=1 minute, rotor operating time=4 minutes, andtemperature=100° C.

Vulcanization Characteristics

Determined based on ASTM D6204, using RPA 2000 Alpha Technologies rubberprocessing analyzer, operating time=30 minutes, and temperature=170° C.

Evaluation and Measurement of Properties of Rubber Composition

A vulcanized rubber compound was prepared using a polymer obtained ineach of Examples, and was measured for the following test parameters.

i) Tire predictors (tan δ at 60° C., tan δ at 0° C., tan δ at −10° C.)

A vulcanized rubber compound was used as a test sample and measured forthis parameter, using a dynamic mechanical analyzer (DMA 450+MetraviB)in single shear mode under the conditions of dynamic strain=2%,frequency=10 Hz, in the temperature range of from −70 to 70° C., with aheating rate of 2.5 K/min.

ii) Rebound resilience

Determined based on ISO 4662.

Table 1 shows the characterization results for the four samplessynthesized for this study.

TABLE 1 M_(n) M_(w) Vinyl Styrene % F Ex- [g/ [g/ M_(w)/ content content[% MV Tg ample mol] mol] M_(n) [%]¹ [%] wt.] [1 + 4] [° C.] 1b 222, 318,1.43 62.1 21.3 0 60.3 −26.1 (comp.) 300 800 2b 229, 316, 1.38 61.5 21.10.39 57.3 −24.4 100 200 3b 226, 319, 1.41 62.3 21.7 0.65 62.4 −25.2 400900 4b 185, 329, 1.77 61.9 21.5 0.62 51.8 −23.4 800 100 ¹Based on1,3-butadiene content

Compounding

Using the rubbers obtained in Examples 2b, 3b, 4b and ComparativeExample 1b, respectively, compounding was made according to the“compounding recipe of rubber composition” shown in Table 2. Thecompounding of the solution styrene-butadiene rubber, fillers, andrubber additives was performed in a Banbury type of internal mixer (350EBrabender GmbH& Co. KG) and on a lab-sized two roll mill. The rubbercompounds were mixed in two different stages and the final pass wascompleted on a two roll mill. The first stage was used to mix thepolymer with oil, silica, silane coupling agent, 6PPD and activators inseveral steps. The second stage was to further improve the distributionof the silica along with adding of carbon black, then the compound wasallowed to sit for 24 hours. In order to be conditioned for the finalpass, the rubber compound was allowed to condition for four hours. Thefinal mixing was performed on a two roll mill. The last step was used toadd the cure packages. Then, each compound was vulcanized at 170° C.,for T_(95+1.5) minutes (based on RPA results), to obtain vulcanizates.Each vulcanized rubber compound was evaluated and measured for theabove-mentioned curing characteristics, tire predictors and reboundresilience. The results are shown in Table 3.

TABLE 2 Component phr SBR 75 Polybutadiene rubber¹ 25 Silica² 80 CarbonBlack³ 10 Stearic acid 2 Zinc oxide 3 Oil extender⁴ 37.5 6PPD⁵ 2Bis[3-(triethoxysilyl)propyl]tetrasulfide⁶ 6.4N-tert-butyl-2-benzothiazole 1.7 sulfenamide⁷ 1,3-Diphenylguanidine⁸ 2Sulphur 1.5 ¹Synteca 44, a product of Synthos ²Zeosil 1165MP, a productof Solvay ³ISAF-N234, a product of Cabot Corporation ⁴VivaTec 500, aproduct of Klaus Dahleke KG ⁵VULKANOX 4020/LG, a product of Lanxess ⁶Si69, a product of Evonik ⁷LUVOMAXX TBBS, a product of Lehmann & Voss &Co. KG ⁸DENAX, a product of Draslovka a.s.

TABLE 3 Rebound Rebound resilience resilience (23° C.), (70° C.), tan δtan δ, tan δ, Example [%] [%] (60° C.) (0° C.) (−10° C.) 1c 32.2 54.90.192 0.514 0.663 (comp.) 2c 34.8 60.7 0.145 0.646 0.756 3c 37.7 66.10.134 0.644 0.788 4c 38.2 67.3 0.143 0.682 0.949

It is apparent from these results that in a silica mix, as judged basedon the properties in the vulcanized state, SSBR 3b according to theinvention imparts to the corresponding rubber composition 3creinforcement properties which are superior to those obtained with thecontrol SSBR 1b and with the other SSBR 2b according to the invention.Moreover, the data in Table 3 shows that SSBR 4b obtained in continuouspolymerization has better reinforcement properties compared to controlSSBR 1b and SSBR 2b.

Furthermore, the tire predictors of rubber composition 3c according tothe invention are improved relative to those of the control rubbercomposition 1c and of the rubber compositions 2c and 4c (in terms ofrolling resistance) according to the invention. Moreover, said tirepredictors are improved for rubber composition 2c according to theinvention relative to the control rubber composition 1c. Furthermore,tire predictors are improved for rubber composition 4c according to theinvention relative to the control rubber composition 1c; additionally,ice traction and dry traction properties are improved relative to thoseof rubber compositions 1c, 2c, and 3c.

II.2 Application of Functionalized Myrcene in CoordinationPolymerization

In order to provide more details about the synthesis and properties ofelastomers produced according to the present invention, functionalizedbutadiene homopolymer with functional groups are described in Examples6b and 8b below, and are compared with a non-functionalized homopolymeras described in Comparative Examples 5b and 7b. The amounts of startingmaterials used in these examples are listed in Table 4. The measurementmethods and evaluation methods of properties are shown below.

Polymerization (for Additional Information, See Also the AboveInformation Relating to Anionically Obtained Polymers)

For catalyst composition and procedure, see the following publications:

1. Lars Friebe, Oskar Nuyken and Werner Obrecht, “A Comparison ofNeodymium Versatate, Neodymium Neopentanolate and NeodymiumBis(2-ethylhexyl)phosphate in Ternary Ziegler Type Catalyst Systems WithRegard to their Impact on the Polymerization of 1,3-Butadiene”, in J.Macromol. Sci. A., (2005), 42, 7, 839-851.

2. Friebe, L., Nuyken, O., Windisch, H., and Obrecht, W. “Polymerizationof 1,3-butadiene initiated by neodymium versatate/diisobutylaluminumhydride/ethylaluminum sesquichloride: Kinetics and conclusions about thereaction mechanism”, in Macromol. Chem. Phys., (2002), 203, 8,1055-1064.

General Polymerization Description:

A twenty litre reactor was filled with dry 1,3-butadiene and dry solvent(cyclohexane), and functionalized myrcene of Example 1a, and heated to60° C. Then, catalyst was added in the following sequence: neodymiumbis(2-ethylhexyl)phosphate (Nd P), diisobutylaluminum hydride (DIBAH)(both 0.1 mol/L solutions in cyclohexane). Polymerization was started byaddition of ethylaluminum sesquichloride (EASC) (1.0 mol/L solution incyclohexane). The solution inside the reactor was heated andcontinuously stirred during the whole process. The temperature of thereaction mixture was kept between 60 and 90° C. The reaction solutionwas terminated, using nitrogen-purged isopropyl alcohol, and was rapidlystabilized by the addition of2-methyl-4,6-bis(octylsulfanylmethyl)phenol (at 1.0 phr polymer).

The polymers were recovered by a conventional recovery operation usingsteam stripping of the solvent and were dried in a stream of hot air.

Details of the reaction conditions, of the used recipes andcharacteristics of the obtained polymers are included in Table 4 below.

TABLE 4 Reactions conditions and obtained polymers characteristics(coordination polymerization), where n_(M)/n_(Nd)- represents the molarratio of monomer to neodymium, n_(Cl)/n_(Nd)-represents the molar ratioof chloride to neodymium, n_(DIBAH)/n_(Nd)-represents the molar ratio ofDIBAH to neodymium, F%-represents content by weight percent offunctionalized myrcene in the polymer chains. Reaction conditions GPCresults DSC Cyclo- 1,3- Mn Mw FTIR results [%] results T_(init) hexanebutadiene n_(M)/ n_(Cl)/ n_(DIBAH)/ [kg/ [kg/ Mw/ 1,4- 1,4- Tg|, % F MVEx . [° C.] [g] [g] n_(Nd) n_(Nd) n_(Nd) mol] mol] Mn Vinyl cis trans °C. [% wt.]¹ [1 + 4] 5b 60 12000 1500 9250 2 6 156.3 292.3 1.87 0.2 97.82.0 −105 0 66 6b 60 12000 1500 9250 2 7 148.1 265.1 1.79 0.3 98.0 1.7−105 0.98 60 7b 60 12000 1500 9250 2 8 119.2 243.2 2.04 0.3 97.6 2.1−104 0 43 8b 60 12000 1500 9250 2 8 1217 244.6 2.01 0.2 97.8 2.0 −1040.96 45 ¹Theoretical value, some signals from catalyst overlap signalsfrom functionalized diene

Characterization (Additional Information, See Also the Above InformationRelating to Anionically Obtained Polymers)

Vinyl content, cis-1,4 content, trans-1,4 content (%)

The microstructure of butadiene rubber was determined by infraredspectroscopy (Thermo Scientific Nicolet Is10). The following peaks wereused for quantitative determination of the poly(butadiene)microstructure:

735 cm⁻¹ (δ(cis-R—CH═CR—H), →cis-1,4, ε=0.192),

912 cm⁻¹ (δ(R—CH═CH—H), →vinyl (1,2), ε=1.0),

965 cm⁻¹ (δ(trans-R—CH═CR—H), →trans-1,4, ε=0.769).

The methodology is described in:

1. M. Kraft, Struktur and Absorptionsspektroskopie der Kunststoffe, VCH,Weinheim 1973, p. 93; and

2. E. O. Schmalz, W. Kimmer, Z. Anal. Chem. 1961, 181, 229.

Evaluation and Measurement of Properties of Vulcanized RubberComposition (Additional Information, See Also the Above InformationRelating to Anionically Obtained Polymers)

A vulcanized rubber compound was produced using a polymer obtained ineach of the examples, and was measured for the following test parameters

i) Tire predictors (tan δ at 60° C., tan δ at 0° C., tan δ at −10° C.,J″ at 30° C.)

A vulcanized rubber composition was used as a test sample and measuredfor this parameter, using a dynamic mechanical analyzer (DMA 450+MetraviB) in shear mode under the conditions of tensile strain=2%,frequency=10 Hz, in a temperature range of from −80 to 80° C., with aheating rate of 2.5 K/min.

ii) Rebound resilience

Determined based on ISO 4662

iii) Reinforcement Factor

Expressed as ratio between Modulus 300% and Modulus 100%, Determinedbased PN-ISO 37:2007 using Zwick/Roel Z005

iv) Silica dispersion

Determined based ISO 1134 C, D, E; ASTM D7723, using disperGRADER AlphaTechnologies

Compounding (Additional Information, See Also the Above InformationRelating to Anionically Obtained Polymers)

Using the rubbers as obtained in Examples 6b and 8b and ComparativeExamples 5b and 7b, respectively, compounding was made according to thecompounding recipe as shown in Table 5. The compounding of the solutionstyrene-butadiene rubber, fillers, and rubber additives was performed ina Farrel type of internal mixer (Mixer Farrel BR+1600) and on a labsized two roll mill. The rubber compounds were mixed in three differentstages, first two on internal mixer, and third one (final pass) wascompleted on a two roll mill.

The first stage was used to mix the rubbers with oil, silica, silanecoupling agent, 6PPD and activators in several steps. The second stagewas performed to further improve the distribution of the silica alongwith adding of carbon black, then the compound was conditioned for 24hours. The final mixing was performed on a two roll mill. The last stepwas used to add the cure packages. Then, each compound was vulcanized at170° C., for T_(95+1.5) minutes (based on RPA results), to obtainvulcanizates. Each vulcanized rubber compound was evaluated and measuredfor the above-mentioned curing characteristics, Payne effect and tirepredictors. The results are shown in Table 6.

TABLE 5 Mixing Component phr stage SBR¹ 52 1 Polybutadiene rubber 48 1Silica² 80 1 Carbon Black³ 5 2 Stearic acid 2 1 Zinc oxide 2 1 Oilextender⁴ 28 1 6PPD⁵ 2 1 Antioxidant⁶ 2 1 Wax⁷ 2 1Bis[3-(triethoxysilyl)propyl]tetrasulfide⁸ 6.4 1N-tert-butyl-2-benzothiazole sulfenamide⁹ 1.6 3 1,3-Diphenylguanidine¹⁰2 3 Sulphur 1.5 3 ¹Syntion 2150, a product of Synthos R&D,specification: non functionalized rubber, Mn ~202 kg/mol, Mw ~395kg/mol, Mw/Mn = 1.95, styrene content 21.5%, vinyl 50.6% (/polymer), Tg~−25° C., ²Zeosil 1165MP, a product of Solvay, ³ISAF-N234, a product ofCabot Corporation, ⁴VivaTec 500, a product of Klaus Dahleke KG,⁵VULKANOX 4020/LG, a product of Lanxess, ⁶TMQ luvomaxx, ⁷MC Wax 721, ⁸Si69, a product of Evonik, ⁹LUVOMAXX TBBS, a product of Lehmann & Voss &Co. KG, ¹⁰DENAX, a product of Draslovka a.s.

TABLE 6 J″ G′[Pa|]/ RI % F MV tan 6 (30° C.)², E′ (−20° C.] Rebound⁴ at(S300%/ Silica Ex [% wt.] [1 + 4] (60° C.)¹ [Pa⁻¹] [MPa] T_(70°) _(C.)S100%)⁵ Dispersion⁶ [%] 5c 0 66 0.188 4.63E−08 1.62E+07 59 4.3 81 6c0.98 60 0.162 5.09E−08 1.18E+07 62 4.7 93 7c 0 43 0.190 5.07E−081.62E+07 57 4.2 79 8c 0.96 45 0.157 4.81E−08 1.26E+07 63 4.8 92 ¹Rollingresistance (lower is better) ²Dry traction (higher is better) ³WinterTraction (lower is better) ⁴Rebound at 70° C. (higher is better)⁵Reinforcement index (higher is better) ⁶Silica dispersion (higher isbetter)

The rubbers as obtained in Examples 6c and 8c and Comparative Examples5c and 7c, respectively, were examined and compared to each other(functionalized vs. non-functionalized), see the results presented inTable 6.

Example 5c was compared with Example 6c, and Example 7c with Example 8c,since they correspond to similar Mooney ranges, namely higher (58, 64)and lower (44, 51).

In each case, tire predictors obtained from DMA, such as rollingresistance, dry traction, winter traction are improved when comparingfunctionalized (Ex. 6c, 8c-Table 6) and nonfunctionalized (Ex. 5c,7c-Table 6) rubber, the same is true with respect to rebound at hightemperature. The reinforcement index, the ratio of modulus 300% tomodulus 100%, was also found to be increased, as well as much highersilica dispersion (dispeGRADER). This confirmed a much higherinteraction between functionalized cis-polybutadiene rubber and filler(silica), as compared to the use of non-functionalized rubber.

While certain representative embodiments and details have been shown forthe purpose of illustrating the subject invention, it will be apparentto those skilled in this art that various changes and modifications canbe made therein without departing from the scope of the subjectinvention, which scope is defined by the following claims.

1. A method for the preparation of a functionalized conjugated dieneselected from the group of compounds of formula (IIIa), (IIIb), (IIIc)

wherein R is an organylene group optionally containing one or moreheteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom, and the starting conjugated diene selectedfrom the group of compounds of formula (Ia), (Ib), (Ic)

from which the functionalized conjugated diene of formula (IIIa),(IIIb), (IIIc) is derived, has at least 10 carbon atoms, R¹ is selectedfrom i) a single bond, ii) one or more of an oxygen atom, a sulfur atom,a group NR⁶, and a group SiR⁷R⁸; and iii) an organylene group optionallycontaining one or more selected from an oxygen atom, a sulfur atom, agroup NR⁶, and a group SiR⁷R⁸; R², R³, R⁶, R⁷, R⁸ can be the same ordifferent and represent an organyl group optionally containing one ormore heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom; and i) R⁴ and R⁵ can be the same or differentand each R⁴ and R⁵ independently represents an organyl group optionallycontaining one or more heteroatoms selected from a silicon atom, anoxygen atom, a sulfur atom, and a nitrogen atom; or ii) R⁴ and R⁵ arebonded to each other to form a heterocyclic ring containing the nitrogenatom and at least one carbon atom and, optionally, one or moreheteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom,and a nitrogen atom, the method comprising reacting, under Grignardconditions, a conjugated diene halide selected from the group ofcompounds of formula (IIa), (IIb), (IIc)

wherein Y¹ is selected from fluorine, chlorine, bromine, and iodineatoms (and Y¹ is preferably a chlorine atom), with a compound of formula(IV)

wherein Y² is selected from fluorine, chlorine, bromine, and iodineatoms.
 2. A method for the preparation of a functionalized conjugateddiene selected from the group of compounds of formula (IIIa), (IIIb),(IIIc)

wherein R is an organylene group optionally containing one or moreheteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom, and the starting conjugated diene selectedfrom the group of compounds of formula (Ia), (Ib), (Ic)

from which the functionalized conjugated diene of formula (IIIa),(IIIb), (IIIc) is derived, has at least 10 carbon atoms, R¹ is selectedfrom i) a single bond, ii) one or more of an oxygen atom, a sulfur atom,a group NR⁶, and a group SiR⁷R⁸; and iii) an organylene group optionallycontaining one or more selected from an oxygen atom, a sulfur atom, agroup NR⁶, and a group SiR⁷R⁸; R², R³, R⁶, R⁷, R⁸ can be the same ordifferent and represent an organyl group optionally containing one ormore heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom; and i) R⁴ and R⁵ can be the same or differentand each R⁴ and R⁵ independently represents an organyl group optionallycontaining one or more heteroatoms selected from a silicon atom, anoxygen atom, a sulfur atom, and a nitrogen atom; or ii) R⁴ and R⁵ arebonded to each other to form a heterocyclic ring containing the nitrogenatom and at least one carbon atom and, optionally, one or moreheteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom,and a nitrogen atom, the method comprising A) reacting, under Grignardconditions, a conjugated diene halide selected from the group ofcompounds of formula (IIa), (IIb), (IIc)

wherein Y¹ is selected from fluorine, chlorine, bromine, and iodineatoms (and Y¹ is preferably a chlorine atom), with a compound of formula(V)

wherein Y² and Y³ are independently selected from fluorine, chlorine,bromine, and iodine atoms, and preferably Y² and Y³ are each chlorineatoms, to result in a compound of formula (VIa), (VIb), (VIc)

and B) reacting the compound of formula (VIa), (VIb), (VIc) with anamide of formula (VII)

wherein M is an alkali metal selected from lithium, sodium, andpotassium, and M is preferably sodium.
 3. A functionalized conjugateddiene selected from the group of compounds of formula (IIIa), (IIIb),(IIIc)

wherein R is an organylene group optionally containing one or moreheteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom, and the starting conjugated diene selectedfrom the group of compounds of formula (Ia), (Ib), (Ic)

from which the functionalized conjugated diene of formula (IIIa),(IIIb), (IIIc) is derived, has at least 10 carbon atoms, R¹ is selectedfrom i) a single bond, ii) one or more of an oxygen atom, a sulfur atom,a group NR⁶, and a group SiR⁷R⁸; and iii) an organylene group optionallycontaining one or more selected from an oxygen atom, a sulfur atom, agroup NR⁶, and a group SiR⁷R⁸; R², R³, R⁶, R⁷, R⁸ can be the same ordifferent and represent an organyl group optionally containing one ormore heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom; and i) R⁴ and R⁵ can be the same or differentand each R⁴ and R⁵ independently represents an organyl group optionallycontaining one or more heteroatoms selected from a silicon atom, anoxygen atom, a sulfur atom, and a nitrogen atom; or ii) R⁴ and R⁵ arebonded to each other to form a heterocyclic ring containing the nitrogenatom and at least one carbon atom and, optionally, one or moreheteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom,and a nitrogen atom.
 4. The functionalized conjugated diene of claim 3,wherein R¹ is i) a single bond.
 5. The functionalized conjugated dieneof claim 3, wherein R², R³, R⁶, R⁷, and R⁸ are the same or different andrepresent a linear or branched, saturated or unsaturated hydrocarbylgroup, preferably wherein R², R³, R⁶, R⁷, and R⁸ are the same ordifferent and represent a linear or branched alkyl, aryl, or alkarylgroup, more preferably wherein R², ^(R3), ^(R6), R⁷, and R⁸ are the sameor different and represent CH₃ or C₆H₅, in particular wherein R², R³,R⁶, R⁷, and R⁸ all represent CH₃.
 6. The functionalized conjugated dieneof claim 3, wherein R⁴ and R⁵ are the same and represent a linear,branched or cyclic, saturated or unsaturated alkyl group, preferablywherein R⁴ and R⁵ are the same and represent —CH(CH₃)₂ or CH₃, morepreferably wherein R⁴ and R⁵ are the same and represent —CH(CH₃)₂. 7.The functionalized conjugated diene of claim 3, wherein R is a linear orbranched, saturated or unsaturated hydrocarbylene, hydrocarbylidene, orhydrocarbylidyne group, preferably wherein R is a branched, unsaturatedhydrocarbylene group, more preferably wherein the starting conjugateddiene of formula (Ia), (Ib), (Ic) is selected from terpenes and4,8-dimethyl-1,3,7-nonatriene, most preferably wherein the terpene isselected from myrcene and ocimene, in particular wherein the terpene ismyrcene selected from α-myrcene and β-myrcene.
 8. The functionalizedconjugated diene of claim 7, which is a myrcene derivative of formula(VIII), (IX), or (X)

preferably wherein the myrcene derivative is of formula (VIIIa), (IXa),or (Xa)


9. Use of one or more functionalized conjugated dienes of claim 3, inthe production of an elastomeric copolymer.
 10. The use of claim 9,wherein the elastomeric copolymer comprises, in addition to one or moreunits derived from the one or more functionalized conjugated dienesselected from the group of compounds of formula (IIIa), (IIIb), (IIIc),units derived from one or more conjugated diene monomers, preferablywherein the conjugated diene monomer is selected from 1,3-butadiene,isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene,2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene,2-phenyl-1,3-butadiene, and 4,5-diethyl-1,3-octadiene, more preferablywherein the conjugated diene monomer is selected from 1,3-butadiene andisoprene, in particular wherein the conjugated diene monomer is1,3-butadiene.
 11. The use of claim 9, wherein the production of theelastomeric copolymer is by anionic polymerization or by coordinationpolymerization.
 12. The use of claim 9, wherein the elastomericcopolymer further comprises units derived from one or more vinylaromatic monomers, preferably wherein the vinyl aromatic monomer isselected from styrene, 1-vinylnaphthalene, 3-methyl styrene, 3,5-diethylstyrene, 4-propylstyrene, 2,4,6-trimethylstyrene,4-dodecylstyrene, 3-methyl-5-n-hexylstyrene, 4-phenylstyrene,2-ethyl-4-benzylstyrene, 3,5-diphenylstyrene, 2,3,4,5-tetraethylstyrene,3-ethyl-1-vinylnaphthalene, 6-isopropyl-1-vinylnaphthalene,6-cyclohexyl-1-vinylnaphthalene, 7-dodecyl-2-vinylnaphthalene, andα-methyl styrene, more preferably wherein the vinyl aromatic monomer isselected from styrene, 3-methylstyrene and α-methylstyrene, inparticular wherein the vinyl aromatic monomer is styrene.
 13. The use ofclaim 9, wherein the amount of units derived from the one or morefunctionalized conjugated dienes selected from of the group of compoundsof formula (IIIa), (IIIb), (IIIc) is in a range of from 0.05 to 5 wt. %,based on the weight of the elastomeric copolymer, more preferably in arange of from 0.2 to 1.5 wt. %, most preferably in a range of from 0.4to 1.2 wt. %, e.g. in a range of from 0.6 to 1.0 wt. %, such as about0.8 wt. %.
 14. The use of an alkali metal salt derivative of afunctionalized conjugated diene selected from the group of compounds offormula (IIIa), (IIIb), (IIIc)

wherein R is an organylene group optionally containing one or moreheteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom, and the starting conjugated diene selectedfrom the group of compounds of formula (Ia), (Ib), (Ic)

from which the functionalized conjugated diene of formula (IIIa),(IIIb), (IIIc) is derived, has at least 10 carbon atoms; R¹ is selectedfrom i) a single bond, ii) one or more of an oxygen atom, a sulfur atom,a group NR⁶, and a group SiR⁷R⁸; and iii) an organylene group optionallycontaining one or more selected from an oxygen atom, a sulfur atom, agroup NR⁶, and a group SiR⁷R⁸; R², R³, R⁶, R⁷, R⁸ can be the same ordifferent and represent an organyl group optionally containing one ormore heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom; and i) R⁴ and R⁵ can be the same or differentand each R⁴ and R⁵ independently represents an organyl group optionallycontaining one or more heteroatoms selected from a silicon atom, anoxygen atom, a sulfur atom, and a nitrogen atom; or ii) R⁴ and R⁵ arebonded to each other to form a heterocyclic ring containing the nitrogenatom and at least one carbon atom and, optionally, one or moreheteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom,and a nitrogen atom, as initiator for the anionic copolymerization ofone or more conjugated diene monomers, optionally one or more vinylaromatic monomers, and optionally one or more functionalized conjugateddienes selected from the group of compounds of formula (IIIa), (IIIb),(IIIc).
 15. A process for the production of a copolymer componentcomprising coupled copolymer and terminally modified copolymer, theprocess comprising the following steps: (1) providing an initiatorcomponent, wherein the initiator component preferably comprises one ormore alkali metal salt derivatives of a one or more functionalizedconjugated dienes selected from the group of compounds of formula(IIIa), (IIIb), (IIIc)

wherein R is an organylene group optionally containing one or moreheteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom, and the starting conjugated diene selectedfrom the group of compounds of formula (Ia), (Ib), (Ic)

from which the functionalized conjugated diene of formula (IIIa),(IIIb), (IIIc) is derived, has at least 10 carbon atoms R¹ is selectedfrom i) a single bond, ii) one or more of an oxygen atom, a sulfur atom,a group NR⁶, and a group SiR⁷R⁸; and iii) an organylene group optionallycontaining one or more selected from an oxygen atom, a sulfur atom, agroup NR⁶, and a group SiR⁷R⁸; R², R³, R⁶, R⁷, R⁸ can be the same ordifferent and represent an organyl group optionally containing one ormore heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom; and i) R⁴ and R⁵ can be the same or differentand each R⁴ and R⁵ independently represents an organyl group optionallycontaining one or more heteroatoms selected from a silicon atom, anoxygen atom, a sulfur atom, and a nitrogen atom; or ii) R⁴ and R⁵ arebonded to each other to form a heterocyclic ring containing the nitrogenatom and at least one carbon atom and, optionally, one or moreheteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom,and a nitrogen atom, wherein the alkali metal is selected from lithium,sodium, and potassium; (2) contacting a monomer component comprising i)one or more functionalized conjugated dienes selected from the group ofcompounds of formula (IIIa), (IIIb), (IIIc), ii) one or more conjugateddiene monomers and iii) optionally one or more vinyl aromatic monomers,with the initiator component, to initiate anionic copolymerization; (3)continuing copolymerization, to result in a copolymer; (4) optionallycontinuing copolymerization of the copolymer, in the presence of one ormore functionalized monomers, to result in a functionalized copolymer;(5) coupling a part of the copolymer of step (3) or the functionalizedcopolymer of step (4) with one or more coupling agents, to result incoupled copolymer; and (6) terminally modifying a part of the copolymerof step (3) or the functionalized copolymer of step (4) with one or moreterminal modifying agents, to result in terminally modified copolymer.16. A process for producing an elastomeric copolymer comprisingsubjecting i) one or more functionalized conjugated dienes selected fromthe group of compounds of formula (IIIa), (IIIb), (IIIc)

wherein R is an organylene group optionally containing one or moreheteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom, and the starting conjugated diene selectedfrom the group of compounds of formula (Ia), (Ib), (Ic)

from which the functionalized conjugated diene of formula (IIIa),(IIIb), (IIIc) is derived, has at least 10 carbon atoms; R¹ is selectedfrom i) a single bond, ii) one or more of an oxygen atom, a sulfur atom,a group NR⁶, and a group SiR⁷R⁸; and iii) an organylene group optionallycontaining one or more selected from an oxygen atom, a sulfur atom, agroup NR⁶, and a group SiR⁷R⁸; R², R³, R⁶, R⁷, R⁸ can be the same ordifferent and represent an organyl group optionally containing one ormore heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom; and i) R⁴ and R⁵ can be the same or differentand each R⁴ and R⁵ independently represents an organyl group optionallycontaining one or more heteroatoms selected from a silicon atom, anoxygen atom, a sulfur atom, and a nitrogen atom; or ii) R⁴ and R⁵ arebonded to each other to form a heterocyclic ring containing the nitrogenatom and at least one carbon atom and, optionally, one or moreheteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom,and a nitrogen atom, ii) one or more conjugated diene monomers, and iii)optionally one or more vinyl aromatic monomers to anionic polymerizationconditions, preferably wherein the anionic polymerization conditionsinclude initiating the polymerization with an alkali metal saltderivative of the one or more functionalized conjugated dienes offormula (IIIa), (IIIb), (IIIc), wherein the alkali metal is selectedfrom lithium, sodium, and potassium.
 17. A process for producing anelastomeric copolymer comprising subjecting i) one or morefunctionalized conjugated dienes selected from the group of compounds offormula (IIIa), (IIIb), (IIIc)

wherein R is an organylene group optionally containing one or moreheteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom, and the starting conjugated diene selectedfrom the group of compounds of formula (Ia), (Ib), (Ic)

from which the functionalized conjugated diene of formula (IIIa),(IIIb), (IIIc) is derived, has at least 10 carbon atoms; R¹ is selectedfrom i) a single bond, ii) one or more of an oxygen atom, a sulfur atom,a group NR⁶, and a group SiR⁷R⁸; and iii) an organylene group optionallycontaining one or more selected from an oxygen atom, a sulfur atom, agroup NR⁶, and a group SiR⁷R⁸; R², R³, R⁶, R⁷, R⁸ can be the same ordifferent and represent an organyl group optionally containing one ormore heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom; and i) R⁴ and R⁵ can be the same or differentand each R⁴ and R⁵ independently represents an organyl group optionallycontaining one or more heteroatoms selected from a silicon atom, anoxygen atom, a sulfur atom, and a nitrogen atom; or ii) R⁴ and R⁵ arebonded to each other to form a heterocyclic ring containing the nitrogenatom and at least one carbon atom and, optionally, one or moreheteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom,and a nitrogen atom, and ii) one or more conjugated diene monomers toZiegler-Natta polymerization conditions.
 18. The process of claim 17,wherein the Ziegler-Natta polymerization conditions include a catalystsystem comprising 1) metal chloride and 2) co-catalyst, preferablywherein the metal chloride 1) is selected from chlorides of one or moreof Ni, Co, Ti, Nd, V, Ti, Zr, and Fe, and the co-catalyst 2) is selectedfrom one or more of aluminium and magnesium alkyl compounds.
 19. Theprocess of claim 17, wherein the Ziegler-Natta polymerization conditionsinclude a catalyst system comprising 1) non-halide metal compound, 2)co-catalyst, and 3) halide donor compound, preferably wherein thenon-halide metal compound 1) is one or more Nd compounds, morepreferably wherein the Nd compound is selected from neodymiumcarboxylates, neodymium alcoholates, neodymium phosphates, neodymiumphosphonates, neodymium allyl compounds, neodymium cyclopentadienylcomplexes, neodymium amides, and neodymium acetylacetonates.
 20. Anelastomeric copolymer comprising repeat units that are derived from A)0.05 wt. % to 5 wt. %, by weight of the copolymer, of one or morefunctionalized conjugated dienes selected from the group of compounds offormula (IIIa), (IIIb), (IIIc)

wherein R is an organylene group optionally containing one or moreheteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom, and the starting conjugated diene selectedfrom the group of compounds of formula (Ia), (Ib), (Ic)

from which the functionalized conjugated diene of formula (IIIa),(IIIb), (IIIc) is derived, has at least 10 carbon atoms, R¹ is selectedfrom i) a single bond, ii) one or more of an oxygen atom, a sulfur atom,a group NR⁶, and a group SiR⁷R⁸; and iii) an organylene group optionallycontaining one or more selected from an oxygen atom, a sulfur atom, agroup NR⁶, and a group SiR⁷R⁸; R², R³, R⁶, R⁷, R⁸ can be the same ordifferent and represent an organyl group optionally containing one ormore heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogenatom, and a silicon atom; and i) R⁴ and R⁵ can be the same or differentand each R⁴ and R⁵ independently represents an organyl group optionallycontaining one or more heteroatoms selected from a silicon atom, anoxygen atom, a sulfur atom, and a nitrogen atom; or ii) R⁴ and R⁵ arebonded to each other to form a heterocyclic ring containing the nitrogenatom and at least one carbon atom and, optionally, one or moreheteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom,and a nitrogen atom; B) 45 wt. % to 99.95 wt. %, by weight of thecopolymer, of one or more conjugated diene monomers; C) 0 wt. % to 50wt. %, by weight of the copolymer, of one or more vinyl aromaticmonomers.
 21. The elastomeric copolymer of claim 20, wherein the amountof B) conjugated diene monomer is 50 to 92 wt. %, by weight of thecopolymer, preferably 60 to 90 wt. %, by weight of the copolymer, inparticular 65 to 80 wt. %, by weight of the copolymer.
 22. Theelastomeric copolymer of claim 20 wherein the vinyl aromatic monomer isselected from styrene, 1-vinylnaphthalene, 3-methylstyrene,3,5-diethylstyrene, 4-propylstyrene, 2,4,6-trimethylstyrene,4-dodecylstyrene, 3-methyl-5-n-hexylstyrene, 4-phenylstyrene,2-ethyl-4-benzylstyrene, 3,5-diphenylstyrene, 2,3,4,5-tetraethylstyrene,3-ethyl-1-vinylnaphthalene, 6-isopropyl-1-vinylnaphthalene,6-cyclohexyl-1-vinylnaphthalene, 7-dodecyl-2-vinylnaphthalene, andα-methylstyrene, preferably wherein the vinyl aromatic monomer isselected from styrene, 3-methylstyrene and α-methylstyrene, inparticular wherein the vinyl aromatic monomer is styrene.
 23. Theelastomeric copolymer of claim 20 wherein the amount of C) vinylaromatic monomer is 8 to 45 wt. %, by weight of the copolymer,preferably 10 to 40 wt. %, by weight of the copolymer, in particular 20to 35 wt. %, by weight of the copolymer.
 24. The elastomeric copolymerof claim 20, comprising less than 1 wt. % C) vinyl aromatic monomer (andpreferably no C) vinyl aromatic monomer), wherein the amount of B)conjugated diene monomer is 95 to 99.95 wt. %, by weight of thecopolymer, preferably 98 to 99.6 wt. %, by weight of the copolymer, inparticular 99.0 to 99.4 wt. %, by weight of the copolymer.
 25. Theelastomeric copolymer of claim 20, wherein the conjugated diene monomeris selected from 1,3-butadiene, isoprene, 1,3-pentadiene,2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene,2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, and4,5-diethyl-1,3-octadiene, more preferably wherein the conjugated dienemonomer is selected from 1,3-butadiene and isoprene, in particularwherein the conjugated diene monomer is 1,3-butadiene.
 26. Theelastomeric copolymer of claim 20, wherein the copolymer comprises unitshaving a linear structure.
 27. The elastomeric copolymer of claim 20,wherein the copolymer comprises units having a branched structure. 28.The elastomeric copolymer of claim 20, wherein the copolymer comprisesunits having a star structure and being produced by the reaction ofmetal-terminated living linear copolymer with one or more couplingagents in anionic polymerization conditions, preferably wherein a. I)the coupling agent is a tin halide coupling agent, preferably whereinthe tin halide coupling agent is tin tetrachloride, or II) the couplingagent is a silicon halide coupling agent, preferably wherein the siliconhalide coupling agent is selected from silicon tetrachloride, silicontetrabromide, silicon tetrafluoride, silicon tetraiodide,hexachlorodisilane, hexabromodisilane, hexafluoro-disilane,hexaiododisilane, octachlorotrisilane, octabromotrisilane,octafluorotrisilane, octaiodotrisilane, hexachlorodisiloxane,2,2,4,4,6,6-hexachloro-2,4,6-trisilaheptane-1,2,3,4,5,6-hexakis[2-(methyldichlorosilyl)ethyl]benzene,and alkyl silicon halides of general formula (XI)R⁶ _(n)—Si—X_(4-n)   (XI), wherein R⁶ is a monovalent aliphatichydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatichydrocarbon group having 6 to 18 carbon atoms; n is an integer of 0 to2; and X can be a chlorine, bromine, fluorine or iodine atom, and/orwherein b. the fraction of units having star structure is between 0 and75%, by weight of the copolymer.
 29. A method for producing a rubbercomprising vulcanizing the elastomeric copolymer according to claim 20in the presence of one or more vulcanizing agents.
 30. A rubber asobtainable according to the method of claim
 29. 31. A rubber compositioncomprising x) a rubber component comprising the rubber according toclaim 30, preferably wherein the rubber composition further comprises y)one or more fillers, more preferably wherein the filler is selected fromthe group consisting of silica and carbon black, most preferably whereinthe rubber composition comprises y) both silica and carbon black. 32.The rubber composition according to claim 31, wherein the amount offiller component y) is 10 to 150 parts by mass relative to 100 parts bymass of the rubber component x) (phr), preferably wherein the amount offiller component y) is 20 to 140 phr, more preferably wherein the amountof filler component y) is 30 to 130 phr.
 33. The rubber compositionaccording to claim 31 wherein the rubber component x) also comprises oneor more further rubbery polymers, preferably wherein the further rubberypolymer is selected from the group consisting of natural rubber,synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber,ethylene-α-olefin copolymer rubber, ethylene-α-olefin-diene copolymerrubber, acrylonitrile-butadiene copolymer rubber, chloroprene rubber,and halogenated butyl rubber.
 34. A tire component comprising the rubbercomposition of claim 33, preferably wherein the tire component is a tiretread.
 35. A tire comprising the tire component of claim 34.